Nitrosulfonylchlorids of ortho-oxycarboxylic acids and of their derivatives.



mcnannxornn, or voiiwriuxnn, NEAR nunnarnrn, am) GSKAR DB-ESSEL, or

INC OF NEW YORK, 13!. 'Z.-, A CORPGRATION OF NEW YUBKJirrrnosoaromonnonmsf orfosrno-ox zcnnsoxrtrc To all'wlwm it may concern:

Be it known that we," RIcHARoKoTnE and mm Dnnssnn, doctors ofphilosophy, chemists, 'citizens of the German Empire, residing at,respectively, Vohwinkel, near- Elberfeldiand Miilheim-on-thefihine,Germany, have invented new and useful Improvements inNitrosulfonylchloridsof Ortho-Oxycarboxylic Acids and of TheirDerivatives, of which the following is a specification.

The present invention relates to the manufacture of valuableintermediate compounds for the production of dyestufls and forthepreparation of pharmaceutical products, which can be obtained by nitrating sulfonylchlorids of ortho-oxyc'arboxylic acid compounds, such assalicylic-para-sul fonylchlorid, meta: cresotinic sulfonylchlorid, thesulfonylchlorid of.the-salicylic-. ,n ethyl ester, etc.

These nitrosulfonylchlorids are generally colorless crystallinecompounds, insoluble in water and generallysoluble in ether, acetone,benzene, chl.o roform, ligroinand glacial acetic acid.

In order to illustrate the new process i more fully the followingexample is given,

the parts being by weight: 236.5 parts of salicylicacid-para-sulfonylchlorid are dissolved While .being cooled in l420..parts of anhydrous sulfuric acid and are nitrated at a temperature offrom 0 to 10 C. with an acid consisting'of 102 parts of nitric acid (40B.) and 148 parts of anhydrous sulfuri'c acid. When the reaction isalmost.

complete the nitroproduct separates for the most part. 'The light yellowcolored pulp is still'sti'rred forsome-time and then oured on ice. a Thenitrosulfonylchlorid is ltered off, washed with cold .Water'and dried ata moderate temperature. .Thisproduct is easily ioluble in ether andacetone, ,diflicultly soluble in benzene, ligroin' and Chl0-. reform. Itcrystallizes from toluene and- I chlorobenzene in colorless needlesmelting 181 .to 182 G. wherebya slow evoacres .AND or return nnmvarzvns.

1,1251%, sp ifi i of Letters Patent Patented Jan. is, rare; m Drawing.Application filed May 12, 1914. Serial No. 838,094.

, "T no w-coon cHs -k colorless crystals 218 0.; salicylic-methylesterof the formula:

; on i soici crystalline needles melting'at from to 133 0. Insteadof'the nitric acid men tionedin the example other nitrating' agents suchas salts of the nitric acid can he used.

1. The herein described nitrosul'ionylchloride of ortho-oxycarboxylicacid compounds, hich are'genera'lly colorless crystallme compounds,insoluble in Water and, generally soluble. 1n ether, acetone,--hen'zene,

chloroform, ligroin, glacial acetic acid and melting-at from 2'1! to thenitros'ulfonylchlorid of the being valuable intermediate produc'ts'forthe production of dyestuffs and for the prep aration of pharmaceuticalcompounds, substantially as described.

2. The herein described nitrosulfonyl chlorids of salicylic acidcompounds, Wllmll are ounds, insoluble in water and generally generallycolorless crystalline cornsolublein' ether, acetone, benzene, chloro-'form, li'groin, glacial acetic acid and being valuable intermediateproducts for the production of dyestufi's and for the preparation ofpharmaceutical compounds, substantially as described. I

I 3. The herein described nitro-salicylicpara-sulfonylchlorid havingmost probably the formula:

a Not-4, 4

benzene in colorless needles melting at from 1:81 to 182 C. beinginsoluble ln'water, easily soluble in ether and acetone, butdifiicultl'y soluble in benzene, ligroin and chloreform and havingproved to be a valuable intermediate product for the preparation ofdyestufi's and the production of pharmaceutical products, substantiallyas described.

In testimony whereof we have hereunto set'our hands in the presence oftwo subscribing witnesses.

RICHARD KOTHE. 'OSKAR DRESSEL.

Witnesses: Lows VANoonN, HANS BRIjKNER.

